Water-free polishes containing partially neutralized wax-acid paraffin



United States Patent WATER-FREE POLISHES CONTAINING PAR- TIALLY NEUTRALIZED WAX-ACID PAR- AFFIN No Drawing. Application February 15, 1955 Serial No. 488,306

Claims priority, application Germany February 22, 1954 16 Claims. (Cl. 26023) This invention relates to new and useful improvements in liquid, water-free polishes.

In addition to solid polishing pastes, liquid, water-free polishing compositions are being used to an increasing extent for polishing surfaces such as floors, furniture and the like. These liquid polishing compositions have an excellent cleaning power and may easily be applied by spraying.

It has been suggested to produce these liquid polishing compositions from metal stearates such as calcium stearate, slab paraffin, hard wax such as carnauba wax and a solvent. Polishing compositions prepared from the above materials, however, have not proven completely satisfactory since they are non-uniform and will settle upon standing for short periods of time, especially at temperatures above 20 C. In order to produce a film of high 'gloss the polishing compositions generally have a higher wax content of, for example, 520%. With this higher wax content, however, the settling will increase or the composition will be thickly liquid and jellylike, which renders the same unsuitable for use.

One object of this invention is a superior liquid, waterfree wax type polish which is free from the above mentioned disadvantages. This, and still further objects, will become apparent from the following description:

The liquid polishing composition in accordance with the invention comprises an organic solvent solution of a mixture of a wax acid-paraifin, having a portion of its acid content neutralized in the form of an alkali or alkali earth metal soap, with a hard paraffin melting of around 70 C. and/or polyethylene having a molecular weight above 1,000 and below about 10,000.

The term wax acid-parafiin as used herein and in the claims is specifically intended to designate the wax acidparatfin mixtures as are obtained in the known manner from paraffin hydrocarbons by chlorination, dehydrochlorination, catalytic addition of carbon monoxideand hydrogen, subsequent hydrogenation and treatment with molten alkali. The wax acid-paraflin should have a molecular size between C C and preferably C C The wax acid content of the wax acid-paraffin should be preferably about 40-60%. This acid content may be produced by controlling the degree of'chlorination. A portion, and preferably not less than 40%, of the wax acid should be neutralized in the form of an alkali or alkali earth metal soap such as a calcium, sodium, potassium, barium or strontium soap. It has been found advantageous if about 60% of the acid is in the form of this soap. The neutralization as, for example, for formation of the calcium soap may be effected with caustic lime.

The initial starting material for the production of the wax acid-parafiin may consist of normally solid hydrocarbons having 23-40 carbon atoms in the molecule and con- 2,871,210 7 Patented Jan. 27 1959 ice bons. Products of this type are, for example, obtained from corresponding fractions from .the catalytic hydrogenation of carbon monoxide, refined lignite paraflins, petroleum .parafiins, preferably oil-free petroleum paraffins. The boiling ranges of these fractions are not critical as long as the number of carbon atoms in the molecule remains within the prescribed limits. Particularly well suited as starting materials are parafiins having an average number of carbon'atoms which ranges between 28 and 35. If the paraffins'have molecular sizes "outside of the range of C -C the ultimate liquid polishing materials produced therefrom will not have satisfactory properties and will, for example, be thickly liquid or jellylike or will settle or thicken after a relatively short period of time.

The chlorination, dehydrochlorination, catalytic addition of carbon monoxide and hydrogen and subsequent hydrogenation and treatment with alkali of the starting hydrocarbons is efiected in the conventional manner under the known reaction conditions.

The partial neutralization of the acid component is effected by saponification with an alkali or alkali earth metal compound. This partial neutralization is effected, for example, by merely contacting the wax acid-parafiin with caustic lime or oxides or hydroxides of sodium, potassium, barium, and/ or strontium. In the case of the formation of the barium or strontium salts it is preferable to first effect partial neutralization with alkali hydroxides such as sodium hydroxides and then to react the reaction product formed in an aqueous solution with barium or strontium salts at temperatures at which the wax is just melted.

The partially neutralized wax acid-paraffin is then mixed with hard paraffin melting above C. and/or polyethylenes having a molecular weight above 1,000 and below about 10,000.

As hard paraffins the so-called hard paralnn obtained from the catalytic hydrogenation of carbon monoxide containing hydrocarbons of this synthesis which boil above 400 C. have been found preferable.

When using the wax acid-paraffin which contains the partially neutralized acid portion in the form of calcium soap, amounts of hard paraifin up to 1.2 parts per part of the wax acid-paraifinrnay be used.

When the wax acid-paraflin is partly saponified with the sodium, potassium, barium or strontium compounds, the mixing proportion with the hard paraflin may be varied within still wider limits. Partially neutralized wax acidparafiin obtained by the treatment of the wax acid-parafiin with sodium or potassium hydroxide are miscible with the hard paraffin in any proportion. When barium or strontium hydroxides are used in the partial neutralization of the acid portion of the wax acid-paraifin, as much as 2.5 parts of hard paraffin can be admixed per part of the wax acid-paraffin.

When using polyethylenes in place of all or a part of the hard paraflin, the mixing proportion of the wax acidparaflin and the :hard parafiin polyethylene or polyethylene component may be varied within wider limits than with the wax mixtures prepared without the addition of polyethylene. In general, an increase in the range of the miscible mixing proportions is obtained with an increasing proportion of polyethylene to hard parafiin. Waxes in which thepartially neutralized wax acid-parafiin is only mixed with polyethylene of a molecular size above 1,000 and below about 10,000 may contain as much as 10 parts by weight of polyethylene per .each

sisting completely or predominantly of aliphatic hydrocarpart of wax acid-paraflin.

Prior to the partial neutralization of the wax acid portion with alkali or alkaline earth compounds, a part of the acid, may be esterified with monohydric or dihydric alcohols. The wax alcohol-paraflin mixture obtained 3 intermediate product in theproduction of the wax acidparafiin of the molecular size C to C or the pure wax alcohol prepared from said wax-alcohol-paraflin by extraction is preferably used as thefm'onohydric alcohol. Glycols such as ethylene glycol or butylene glycol may be used as dihydric alcohols.

The esterification with alcohols to be efiected in accordance with the invention prior to the partial neutralization with alkali or alkaline earth compounds iseffected in the known manner. For this purpose, the wax acidparaffin, while in the molten state as, for example, with the use of small amounts of p-toluene sulfonic acid, is reacted with the corresponding alcohols. Subsequently to the partial esterification with alcohols, a partial neutralization of the residual acid portion is effected with oxides or hydroxides ofalkali or alkaline earths such as caustic lime.

With this working method, one of the components of the wax used for the production of liquid, water-free polishing agents consists, for example, of about 50 parts of paraflins of the molecular size C -C about 20 parts of an ester produced from the wax acid of the molecular size mentioned above and a monohydric or dihydric alcohol, about 15 parts of a potassium, sodium, barium, calcium or strontium soap of the wax acid mentioned above, and of about 15 parts by weight of the Wax acid proper.

The mixture formed from the hard paraflin and/or polyethylene with the wax acid-paraffin having a portion of its wax acid content neutralized in the form of the calcium, sodium, potassium, barium or strontium soap, and which may additionally contain the ester is converted into the liquid, water-free polish by admixture with a suitable organic solvent. The mixture of the hard parafiin and/or polyethylene with the wax acid-paraflin material is, for example, melted and stirred up with a solvent or solvent mixture such as solvent naphtha and turpentine. The mixture is then allowed to slowly cool to room temperature while stirring. It may be of advantage to subject the material thus prepared to a further homogenization in the conventional manner using, for example, conventional emulsifying devices. The liquid polishing compositions generally contain 10-20% of wax in addition to 80 90% of solvent. Very good polishing compositions are obtained if, besides the solvent, only the wax produced in accordance with the invention is used as the wax component. However, slap parafiin, hard paraflin, micro crystalline petroleum paraflins, ozocerite or other waxes may additionally be incorporated (see the following examples).

. The wax" referred to herein is intended to designate the mixture of the hard paraflin and/or polyethylene with the wax acid-paraflin component.

The liquid polishing agents prepared with the wax produced in accordance with the invention are thinly liquid and completely homogeneous even when having a high wax content. They will not settle even after a long storage period, develop deposits neither at the bottom nor at the upper brim of the liquid. Moreover, they are ex tremely temperature-resistant. At C. they are just as thinly liquid and homogeneous in their structure as at 20 C. or even at temperatures of 3040 C. Liquid polishing compositions of the same quality could not be prepared with the previously used waxes. The polishing compositions can, therefore, be applied without any difficulty with the conventional equipment and result in a hard film of high gloss on the floor treated therewith. The gloss numbers are good because the wax contains relatively large portions of hard paraifin.

While the liquid, water-free polishing compositions prepared with the calcium, barium or strontium containing waxes show no separation of solvent even after extended periods of storage, the polishing compositions which contain the sodium or potassium containing waxes may separate some solvent after an extended storage period. Liquid, water-free polishing compositions in accordance with the invention which contain barium containing waxes may have a wax portion of up to 20% without an increase in the pour point above +5 C. Corresponding polishing'compositions containing the calcium containing waxes will have a pour point of about +10 C. v

The following examples are given by way of illustration and not limitation:

Example 1 (a) A slab parafiin obtained from petroleum, containing all of the hydrocarbons of the molecular size C C with the average number of carbon atoms being 35, and having a setting point of 63 C. Was chlorinated with irradiation until 5.1% of chlorine had been absorbed. The chlorination mixture was heated for 6 hours at 300 C. in a glass flask with the addition of 1% of activated carbon while stirring and passing through small amounts of nitrogen. After having filtered off the solid constituents, a product was obtained which had an iodine number of 32 and contained 0.2% of chlorine.

This olefinic hydrocarbon mixture was treated with water gas for 1 hour at -160 C. and a pressure'of -200 kg./ square centimeter in a pressure vessel with stirrer using a cobalt catalyst. The aldehydes thereby formed were subsequently hydrogenated with hydrogen for 1 hour at 180-200 C. and a pressure of 140-150 kg./square centimeter using likewise a cobalt catalyst. After having filtered off the catalyst, a product of weakly yellowish color containing 55% of alcohols was obtained.

The alcohol-paraffin mixture thus obtained Was mixed with 150% of the theoretically required quantity of caustic potash and stirred for 6 hours at 350 C. in a pressure vessel. Thereafter, the reaction product was decomposed with dilute hydrochloric acid. Then it was repeatedly boiled to remove the last residues of mineral acid. After drying, there remained a light yellow wax acid-parafiin mixture which contained 55% of wax acids. While adding small amounts of water, the mixture was stirred up with caustic lime (CaO) at 100140 C. until the free acid content was reduced to 25%. The finished product thus obtained contained 45% of paraifin, 25% of free wax acids, and 30% of calcium soaps.

(b) Equal parts by weight of the partially saponified wax acid-parafiin mixture prepared in accordance with Example 1(a) and of a hard paraflin from the catalytic carbon monoxide hydrogenation containing all of the hydrocarbons of the synthesis boiling above about 450 C. were mixed. This resulted in a wax which had a setting point of 93 C. and a penetration number of 1.8.

(c) 10 parts by weight of the wax obtained according to Example 1(b) were melted and stirred up with 90 parts by weight of a mixture which contained 90% of solvent naphtha (a petroleum distillate boiling between 130 and C.) and 10% of American turpentine. The mixture was cooled to room temperature while stirring. This resulted in a thinly liquid, completely homogeneous polishing composition which, after a storage time of 10 days at room temperature, showed no sediment at the bottom nor deposits at the upper brim of the liquid. The liquid polishing composition had a pour point of 9 C. and was extremely temperature-resistant. After standing for 24 hours at 40 C. it showed no deposits but had completely retained its homogeneous structure.

(d) A liquid polishing composition was prepared in the manner set forth in Example 1(0) from 5 parts by weight of the wax of Example 1(b), 5 parts by Weight of slab paraffin having a setting point of 52 C. and 90 parts by weight of a mixture of solvent naphtha and turpentine (90% of solvent naptha+10% of turpentine). The product had a pour point of -27 C. After standing for 10 days at room temperature, no solvent had separated from the liquid polishing composition and the same showed no sediment at the bottom and no deposits at the upper brim of the liquid. Even after standing for 24 1(b) and 85 parts by weight of a solvent naphtha-turpentine mixture (90% of solvent naphtha+10% of turpentine) were treated in the manner set forth in Example Me). This resulted in a liquid polishing composition of very uniform structure having a pour point of -2 C. When stored at room temperature and at 40 C. it showed the same behavior as the liquid polishing mass according to Example 1(c).

(f) A liquid polishing composition having a pour point of 5 C. was prepared from 7.5 parts by weight of the wax of Example 1(b), 7.5 parts by weight of slab paratfin having a setting point of 52 C., and 85 parts by weight of a solvent naphtha-turpentine mixture (90% solvent naphtha+ 10% turpentine). When stored at room temperature and at 40 C., this polishing composition showed the same behavior as the polishing agent according to Example 1(0).

Example 2 (a) A petroleum slab parafi'in containing all of the hydrocarbons of the molecular size C C with the average number of carbon atoms being 31 and having a setting point of 57 C. was chlorinated until 5.7% of chlorine had been absorbed. After the splitting-cit of hydrogen chloride there was obtained an olefin-parafi'in mixture Which had an iodine number of 36 and contained 0.2% of chlorine. After the catalytic addition of water gas and hydrogenation eliected in the manner set forth in Example 1(a), there was obtained an alcoholparaffin mixture which contained 52% of alcohols.

This alcohol-paraffin mixture was stirred for 6 hours at 350 C. with 130% of the theoretically required quantity of caustic potash. Decomposition with dilute hydrochloric acid, washing and drying resulted in a light yellow wax acid-parafiin mixture containing 52% of wax acids. This wax acid-parafiin mixture was treated with caustic lime (CaO) in such a manner as to obtain a finished product containing 48% of parafiin, 30% of calcium soaps and 22% of free wax acids.

(b) Mixing of equal parts by weight of the partially saponified wax acid-parafiin mixture of Example 2(a) and of a hard paraffin from the catalytic hydrogenation of carbon monoxide containing all of the hydrocarbons from the catalytic carbon monoxide hydrogenation boiling above about 450 C. and having a setting point of 94 C. resulted in a wax which had a setting point of 92 C. and a penetration number of 2.2.

Liquid polishing compositions were prepared from the wax of Example 2(1)), slab paraffin and solvent naphtha-turpentine in the mixing proportions set forth in Examples 1(a) and 10). All of these polishing compositions were thinly liquid and of very uniform structure. The pour points of the products ranged between 14 and -2 C. After standing for 10 days at room temperature, no solvent had separated from the liquid polishing compositions and the same showed no sediment at the bottom and no deposits at the upper brim of the liquid. Even after a storage of 24 hours at 40 C. the polishing compositions showed no deposits and had retained their uniform structures.

(d) Stirring of parts by weight of the wax according to Example 2(b), 5 parts by weight of slab paratfin having a setting point of 52 C., 5 parts by weight of a hard paraffin from the catalytic hydrogenation of carbon monoxide substantially containing only hydrocarbons boiling above about 450 C., and 85 parts by weight of a solvent-naphtha-turpentine mixture (90% solvent naphtha-l-l0% of turpentine) resulted in a completely uniform liquid polishing composition having a pour point of -5 C. When stored at room temperature and at 40 C., this liquid polishing composition showed the same behavior as the polishing composition of Example 6 Example 3 (a) A slab parafiin obtained from scale oil, containing practically only hydrocarbons of the molecular size C C with the average number of carbon atoms being 27 and having a setting points of 53 C. was chlorinated while irradiating until 7% of chlorine had been absorbed. The dehydrochlorination was effected in accordance with Example 1(a). The yellowish olefin-parafi'in mixture contained 0.1% of chlorine and had an iodine number of 30. The reaction conditions in the addition of water gas and the subsequent hydrogenation were those set forth in Example 1(a). After the separation from the cobalt catalyst, there was obtained a light yellow alcoholparaffin mixture containing 43% of alcohol.

This alcohol-parafiin mixture was stirred for 4 hours at 350 C. with 150% of the theoretically required quantity of caustic potash. After decomposition with dilute hydrochloric acid, washing and drying, there remained a mixture which contained 48% of wax acids in addition to parafiins. The wax acid-paraflin mixture was subsequently stirred with caustic lime (CaO) until the free acid content'was reduced to 18%. This resulted in a finished product which contained 52% of paraflin, 30% of calcium soaps and 18% of wax acids.

(b) Equal parts by weight of the partially saponified wax acid-paraflin mixture obtained in accordance with Example 3(a) and of a hard paraffin from the catalytic hydrogenation of carbon monoxide substantially containing only hydrocarbons boiling above about 450 C. were mixed. This resulted in a wax which solidified at 92 C. and had a penetration number of 2.5.

(6) Liquid polishing compositions were prepared from the wax of Example 3(5), slab paraffin and a solvent naphtha-turpentine mixture in the proportions set forth in Examples 1(c) through All of these polishing compositions were thinly liquid and very uniform and had pour points between -30 and -10 C. When stored at room temperature and at 40 C., the liquid polishing compositions showed the same behavior as the products described in Example 2(c).

(d) A liquid polishing composition was prepared in the manner set forth in Example 1(c) from 7.5 parts by weight of the wax of Example 3 (b), 6.0 parts by weight of slab parafiin (setting point 52 C.), 1.5 parts by Weight of ozocerite (Isocerine 1135), and parts by weight of a mixture of solvent naphtha and turpentine of solvent naphtha+l0% of turpentine). The product had a pour point of 10 C. After standing for 10 days at room temperature, no solvent had separated and a sediment at the bottom or a deposit at the upper brim of the liquid had not formed. Even after a storage of 24 hours at 40 C., a sediment had not formed but the product had completely retained its uniformity.

Example 4 (a) Mixing of equal parts by weight of the partially saponified wax acid-parafiin mixture of Example 1(a) and a microcrystalline petroleum parafiin wax having a setting point of 90 C. resulted in a wax which solidified at 88 C. and had a penetration number of 3.5.

(b) The liquid polishing compositions prepared from the wax according to Example 4(a), slab parafiin and a mixture of solvent naphtha and turpentine in the mixing proportions set forth in Examples 1(0) and 1(f) were thinly liquid, uniform and had pour points of between "25 and +2 C. After a storage of 10 days at room temperature, no solvent had separated and neither a sediment at the bottom nor deposits of wax at the upper brim of the liquids had formed. Even after a storage of 24 hours at 40 C. no deposits had formed but the products had completely retained their uniformity.

Example 5 (a) A slab paraflin obtained from petroleum, containmg hydrocarbons of the molecular size 0 43 with the average number of carbon atoms being 28, and having a setting point of 53 C. was chlorinated with irradiation until 6.3% of chlorine had been absorbed. The chlorination mixture, after the addition of 1% of activated carbon, was heated for 6 hours at 300 C. while stirring and passing through small amounts of nitrogen. After having filtered off the solid constituents, there was obtained a product which had an iodine number of 38 and contained 0.2% of chlorine.

The olefinic hydrocarbon mixture, in a pressure Vessel with stirrer, was then treated with Water gas for 1 hour at 140-l60 C. and a pressure of 180200 kg./square centimeter with the use of a cobalt catalyst. hydes thereby formed were subsequently hydrogenated with hydrogen for 1 hour at 180-200 C. and a pressure of 140-150 kg./ square centimeter using a cobalt catalyst. After having filtered off the catalyst, there resulted a weakly yellowish product which contained 50% of alcohols.

The alcohol-parafiin mixture thus obtained was mixed with 130% of the theoretically required quantity of caustic potash and stirred for 6 hours at 350 C. in a pressure vessel. Thereafter, the reaction product was decomposed with dilute hydrochloric acid. Following this, it was repeatedly boiled with water to remove the last residues of mineral acid. After drying, there remained a wax acid-paraffin mixture of light yellow color which contained 50% of wax acids. While adding small amounts of water, it was stirred at l140 C. with sodium hydroxide until the free acid content was reduced to 25%. The finished product thus produced contained 50% of parafiin, 25% of free wax acids, and 25% of sodium soaps.

(b) Equal parts by weight of the partially saponified wax acid-paraflin mixture according to Example (a) and of a hard parafiin from the carbon monoxide hydrogenation containing the hydrocarbons of the synthesis boiling above about 400 C. were mixed. This resulted in a wax which had a setting point of 93 C. and a penetration number of 4.5.

(c) 7.5 parts by weight of the wax of Example 5(1)) and 7.5 parts by weight of petroleum slab paraffin having a setting point of 53 C. were melted, stirred with 85 parts by weight of solvent naphtha (a petroleum distillate boiling between 130 and 190 C.), and cooled to room temperature while stirring. This resulted in a thinly liquid, uniform polishing composition from which about 20% of the solvent separated after standing for 10 days at room temperature. A separation of wax at the bottom or at the upper brim of the liquid did not occur. The liquid polishing composition had a pour point of -5 C. and a good temperature resistance. After standing for 24 hours at 40 C. it had retained its uniformity and separated only about of the solvent as the upper layer.

(d) A liquid polishing composition was prepared in the manner set forth in Example 5(0) from 5 parts by weight of the wax of Example 5(1)), 5 parts by weight of a petroleum slab paraffin wax having a setting point of 53 C., 5 parts by weight of a hard paraffin from the carbon monoxide hydrogenation containing the hydrocarbons of the synthesis boiling above about 400 C., and 85 parts by weight of solvent naphtha. The liquid polishing composition had a pour point of 6 C. and a very uniform structure. When stored at room temperature and at 40 C., it showed the same behavior as the liquid polishing composition of Example 5(0).

Example 6 (a) The wax acid-paraffin mixture of Example 5(a) was stirred with strontium hydroxide and with the addition of small amounts of water at 100-140 C. until the free acid content Was reduced to 23%. The finished The alde-.

product thus produced contained 50% of paraflin, 23% of free wax acids, and 27% of strontium soaps.

(b) Equal parts by weight of the partially saponified wax acid-paratfin mixture produced in accordance with Example 6(a) and of a hard paraffin from the carbon monoxide hydrogenation containing the hydrocarbons of the synthesis boiling above about 400 C. were mixed. This resulted in a wax which had a setting point of 93 C. and'a penetration number of 4.0.

(0) 7.5 parts by weight of the wax of Example 2(b), 7.5 parts by weight of a petroleum slab paraffin having a setting point of 53 C., and 85 parts by weight of solvent naphtha were mixed in the manner set forth in Example 5(0) resulting in a completely uniform liquid polishing composition having a pour point of 6 C. After standing for 10 days at room temperature, no solvent had separated and the liquid showed no wax deposits at the bottom or at its upper brim. After a storage of 24 hours at 40 C., no wax or solvent had separated and the-polishing composition had retained its uniformity.

(d) A liquid polishing composition was prepared by stirring 5 parts by weight of the wax of Example 6(b), 5 parts by weight of a petroleum slab paraffin having a setting point of 53 C., 5 parts by weight of a hard paratfin from the catalytic hydrogenation of carbon monoxide containing the hydrocarbons boiling above about 400 C., and 85 parts by weight of solvent naphtha. The product was very uniform and had a pour point of 5 C. When stored at room temperature and at 40 C., the liquid polishing composition showed the same behavior as the polishing mass of Example 6(c).

Example 7 (a) The wax acid-paraffin mixture of Example 5(a) was stirred with sodium hydroxide until the free acid content was reduced to 23%. The sodium soaps, in aqueous solution, were converted into the barium soaps by adding a dilute barium chloride solution at -90 C. This resulted in a finished product which contained 50% of paraflin, 23% of free wax acid, and 27% of barium soaps.

(b) Mixing of equal parts by weight of the partially saponified wax acid-parafiin mixture of Example 7(a) and of a hard parafiin obtained from the catalytic hydrogenation of carbon monoxide resulted in a wax which had a setting point of 94 C. and a penetration number of 3.5.

(c) All of the liquid polishing compositions prepared from the wax of Example 7(1)), slab parafiin with or without the addition of hard paraffin, and solvent naphtha with the mixing proportions set forth in Examples 5(0) and 5(d) were thinly liquid, of uniform structure, and had pour points of 8 to -10 C. After standing for 10 days at room temperature, no solvent had separated and no wax deposits had formed at the bottom and the upper brim of the liquid. On standing for 24 hours at 40 C., no solvent had separated and the products had retained their uniform structure (d) Stirring up to 20 parts by weight of the wax of Example 7(b) and 80 parts by weight of solvent naphtha resulted in a completely uniform liquid polishing composition which had a pour point of 2 C. When stored at room temperature and 40 C., the liquid polishing composition showed the same behavior as described in Example 7(0) above.

Example 8 (a) A slab paraflin obtained from petroleum, containing hydrocarbons of the molecular size C C with the average of carbon atoms being 28, and having a setting point of 53 C. was chlorinated with irradiation until 6.3% of chlorine had been absorbed. The chlorination mixture, with the addition of 1% of active carbon, was

heated for 6 hours at 300 C. while stirring and passing through small amounts of nitrogen. After having filtered off the solid constituents, there was obtained a product which had an iodine number of 38 and contained 0.2% of chlorine.

The olefinic hydrocarbon mixture, in a pressure vessel with stirrer, was then treated with water gas for 1 hour at 140l60 C. and a pressure of 180-200 kg./square centimeter with the use of a cobalt catalyst. The aldehydes thereby formed were subsequently hydrogenated with hydrogen for 1 hour at 180-200 C. and a pressure of 140-150 log/square centimeter using a cobalt catalyst. After having filtered off the catalyst, there resulted a weakly yellowish product which contained 50% of alcohols.

A portion of the alcohol-parafiin mixture thus obtained was mixed with 130% of the theoretically required quantity of caustic potash and stirred for 6 hours at 350 C. in an autoclave with stirrer. Thereafter, the reaction product was decomposed with dilute hydrochloric acid. Following this, it was repeatedly boiled to remove the last residues of mineral acid. After drying, there remained a wax acid-paraffin mixture of light yellow color, which contained 50% of wax acids.

The wax acid-paraffin mixture was esterified with the remaining abovementioned alcohol-paraifin mixture at 120-130 C. with the use of 0.5% of toluene-sulfonic acid. The reaction product contained 50% of parafiin, 20% of of esters and 30% of free wax acids. While adding small amounts of water, it was stirred up at 100-140 C. with suflicient caustic lime to reduce the free acid content to The finished product thus obtained contained 50% of parafiin, 20% of esters, 20% of calcium soaps, and 10% of free wax acids.

(b) Equal parts by weight of the partially saponified and partially esterified wax acid-parafiin mixture prepared in accordance with Example 8(a) and of a hard paraflin from the carbon monoxide hydrogenation containing the hydrocarbons from the synthesis boiling above about 400 C. were mixed. This resulted in a wax which had a setting point of 93 C. and a penetration number of (c) 7.5 parts by weight of the Wax of Example 8(1)) and 7.5 parts by weight of slab parafiin having a setting point of 53 C. were melted, stirred up with 85 parts by weight of solvent naphtha (a petroleum distillate boiling between 130 and 190 C.) and cooled to room'temperature while stirring. This resulted in a completely uniform, thinly liquid polishing composition. On standing for 10 days at room temperature, no solvent had separated and the liquid showed no wax deposits at the bottom and at its upper brim. The liquid polishing mass, the pour point of which was 6 C., was very temperature-resistant. After standing for 24 hours at 40 C., it had retained its uniform structure and no solvent had separated.

Example 9 (a) The wax acid-paraffin mixture of Example 8(a) was esterified withbutylene glycol at temperatures of 110-120 C. using 0.5% of p-toluene sulfonic acid. The reaction product contained 50% of parafiin, 20% of esters, and 30% of free wax acids. It was subsequently stirred up with strontium hydroxide until the free acid content was reduced to 10%. This resulted in a finished product which contained 50% of parafiin, 30% of esters, 20% of strontium soaps, and 10% of free acids.

(b) Equal parts by weight of the partially saponified and partially esterified wax acid-parafiin mixture prepared in accordance with Example 9(a) and of a hard paraffin from the carbon monoxide hydrogenation containing the hydrocarbons of the synthesis boiling above about 400 C. were mixed. This resulted in wax which had a setting point of 92 C. and a penetration number of 5.0.

(c) Stirring up of 7.5 parts by weight of the wax of Example 9(b), 7.5 parts by weight of slab paraffin hav- -10 ing a setting point of 53 C1, and parts by weight of solvent naphtha resulted in a completely uniform, liquid polishing compositionwhich had a pour point of -5 C. When stored at room temperature and at 40 C., the liquid polishing composition showed the same behavior as described in Example 8(0).

Example 10 (a) The wax acid-paraffin mixture of Example 8(a) was esterified with butylene glycol at temperatures of 1l0-120 C. with the use of 0.5% of p-toluene-sulfonic acid. The reaction product contained 50% of paraifin, 20% of esters, and 30% of free wax acids. It was subsequently stirred with sufiicient caustic lime to reduce the free acid content to 10%. This resulted in a finished product which contained 50% of paratlin, 30% of esters, 20% of calcium soaps, and 10% of free acids.

(b) Equal parts by weight of the wax of Example 10( 1) and of a polyethylene having a molecular weight of about 3000 were mixed. This resulted in a wax which had a setting point of 93 C. and a penetration number of 5.2.

(c) 7.5 parts by weight of the wax of Example 10(a), 7.5 parts by weight of slab paraffin having a setting point of 53 C., and 85 parts by weight of solvent naphtha were stirred up in the manner set forth in Example 8(0); This resulted in a liquid polishing composition of very uniform structure and having a pour point of 6 C. When stored at room temperature and at 40 C., it showed the same behavior as that of the liquid polishing composition of Example 8(a).

Example II (a) A slab parafiin obtained from petroleum, containing hydrocarbons of the molecular size C -C with the average number of carbon atoms being 28, and having a setting point of 53 C. was chlorinated with irradiation until 6.3% of chlorine had been adsorbed. The chlorination mixture, after the addition of 1% of activated carbon, was heated for 6 hours at 300 C. while stirring and passing through small amounts of nitrogen. After having filtered off the solid constituents, there was obtained a product which had an iodine number of 38 and contained 0.2% of chlorine.

The olefinic hydrocarbon mixture, in a pressure vessel with stirrer, was then treated with water gas for 1 hour at -160 C. and a pressure of -200 kg./square centimeter with the use of a cobalt catalyst. The aldehydes thereby formed were subsequently hydrogenated with hydrogen for 1 hour at 180-200 C. and a pressure of 140-150 kg./square centimeter with the use of a cobalt catalyst. After having filtered off the catalyst, there resulted a weakly yellowish product which contained 50% of alcohols.

The alcohol-paraflin mixture thus obtained was mixed with 130% of the theoretically required quantity of caustic potash and stirred for 6 hours at 350 C. in a pressure autoclave. Thereafter, the reaction product was deeomposed with dilute hydrochloric acid. Following this, 1t was repeatedly boiled with water to remove the last residues of mineral acid. After drying, there remained a wax acid-paratfin mixture of light yellow color which contained 50% of wax acids. While adding small amounts of water, the mixture was stirred at 100-140 C. with suflicient caustic lime to reduce the free acid content to 25%. The finished product thus produced contained 50% of paraflin, 25% of free wax acids, and 25% of calcium soaps.

(b) Equal parts by weight of the partially saponified wax acid-parafiin mixture prepared in accordance with Example 11(a) and of a polyethylene having a molecular weight of about 3000 were mixed. This resulted in a wax which had a setting point of 92 C. and a penetration number of 4.8.

(c) 7.5 parts by weight of the wax of Example 11(b) and 7.5 parts by weight of slab parafiin having a setting point of 53 C. were melted, stirred up with 85 partsby weight of solvent naphtha (a petroleum distillate boiling between 130 and 190 (1.), and cooled to room temperature while stirring. This resulted in a completely uniform, thinly liquid polishing mass. On standing for 10 days at room temperature, no solvent had separated and the liquid showed no wax deposits at the bottom and at its upper brim. The liquid polishing composition had a pour point of C. and was very temperature-resistant. After standing for 24 hours at 40 C., it had retained its uniformity and no solvent had separated.

Example 12 i (:1) Equal parts by weight of a hard parafiin obtained from the carbon monoxide hydrogenation and containing the hydrocarbons boiling above about 400 C. of the synthesis, and a polyethylene having a molecular weight of about 3000 were mixed. To this mixture, equal parts by weight of the partially saponified wax acid-paratfin mixture prepared according to Example 11(a) were added. This resulted in a wax which had a setting point of 93 C. and a penetration number of 4.5.

(b) 7.5 parts by weight of the wax of Example 12(a), 7.5 parts by weight of slab paraffin having a setting point of 53 C., and 85 parts by weight of solvent naphtha were stirred up in the manner set forth in Example 11(0). This resulted in a liquid polishing composition of very uniform structure and having a pour point of -6 C. When stored at room temperature and at 40 C., it showed the same behavior as that of the liquid polishing composition of Example 11(0).

Example 13 (a) The wax acid-parafiin mixture of Example 11(a) was stirred with sodium hydroxide until the free acid content was reduced to 25%. The sodium soaps, in aqueous solution, were converted into the barium soaps by adding a dilute barium chloride solution at 80-90 C. This resulted in a finished product which contained 50% of parafiin, 25% of free wax acid, and 25 of barium soaps.

(b) Equal parts by weight of the partially saponified wax acid-parafin mixture of Example 13(a) and of a polyethylene having a molecular weight of about 3000 were mixed. This resulted in a wax which had a setting point of 93 C. and a penetration number of 4.5.

(c) By stirring up 7.5 parts by weight of the wax of Example 13(b), 7.5 parts by weight of slab paraflin having a setting point of 53 C., and 85 parts by weight of solvent naphtha there was obtained a liquid polishing composition of very uniform structure. It had a pour point of -6 C. When stored at room temperature and at 40 C., it showed the same behavior as that of the liquid polishing composition of Example 11(0).

We claim: I

1. A liquid polishing composition comprising an organic solvent solution of a mixture of a wax acid-paraffin which is obtained from paraflin hydrocarbons by chlorination, dehydrochlorination, catalytic addition of carbon monoxide and hydrogen, subsequent hydrogenation and treatment with molten alkali having a molecular size of about C C and a portion of its acid content neutralized in the form of a metal soap selected from the group consisting of calcium, sodium, potassium, barium and strontium soaps, with a waxymernber selected from the group consisting of hard paraflins melting above about C., polyethylenes having a molecular weight above 1,000 and below about 10,000, and mixtures thereof.

2. Composition according to claim 1 in which said wax acid-paraffin has a molecular size of about C -C 3. Composition according to claim 1 in which said wax acid-parafiin has a wax acid content of about 40-60% and in which at least 40% of said acid content is neutralized in the form of said metal soap.

4. Composition according to claim 3 in which about 60% of the acid content of said Wax acid-paraffin is neutralized in the form of said metal soap.

5 Composition according to claim 3 in which a maximum of 70% of said acid content of said wax acid-paraflin is neutralized in the form of said metal soap.

6. Composition according to claim 1 in which a por tion of the acid content of said wax acid-paraffin is'in the form of an ester with a member selected from the group consisting of monohydric and dihydric alcohols.

7. Composition according to claim 6, in which said wax acid-parafiin contains 40-60% by weight of oxygencontaining compounds and in which 20-40% by weight of said oxygen-containing compounds are esterified and 3050% by weight thereof are present as metal salt and the remainder is present as free acid.

8. Composition according to claim 7 in which said ester is an ester of the wax acid of said Wax acid-paraffin and a wax alcohol.

9. Composition according to claim 7 in which said ester is an ester of the wax acid of said wax acid-parafiin and a glycol selected from the group consisting of ethylene glycol, propylene glycol, and butylene glycol.

10. Composition according to claim 1 in which said organic solvent is a member selected from the group consisting of solvent naphtha, turpentine, and mixtures thereof. 1

11. Composition according to claim 1 in which said last mentioned waxy group member is a hard paraflin present in amount up to 1.2 parts by weight per part by weight of said wax acid-paraffin.

12. Composition according to claim 1 in which said last mentioned waxy group member is a hard parafiin present in amount up to 2.5 parts by weight per part by weight of said wax acid-paraffin.

13. Composition according to claim 11 in which said hard paraffin is a hard parafiin from the catalytic hydro genation of carbon monoxide.

14. Composition according to claim 1 in which said last mentioned Waxy group member is polyethylene present in amount of up to 10 parts by weight per part by weight of wax acid-paraffin.

15. Composition according to claim 1 in which said solvent is present in amount of about -90%.

16. Composition according to claim 15 in which said solventis a member selected from the group consisting of solvent naphtha, turpentine, and mixtures thereof.

References Cited in the file of this patent UNITED STATES PATENTS 2,637,695 McKinley et a1 May 5, 1953 FOREIGN PATENTS 640,476 Great Britain July 19, 1950 981,202 France May 23, 1951 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,871,210 January 27, 1959 Helmut Kolling et al,

It is hereby certified that error appears in the -printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 3, line 4'7, for "slap" read slab column 4, line 50, for "93 C u read 93 C column 6, line 5, for "points" read point column 8, line 62, for "up to read up of column 9, line '72,v for "in Wax" read in a Wax Signed and sealed this 26th day of May 1959'o (SEAL) Attest:

KARL H. AXLINE Attesting Oflicer ROBERT c. WATSON Commissioner of Patents 

1. A LIQUID POLISHING COMPOSITION COMPRISING AN ORGANIC SOLVENT SOLUTION OF A MIXTURE OF A WAX ACID-PARAFIN WHICH IS OBTAINED FROM PARAFFIN HYDROCARBONS BY CHLORINATION, DEHYDROCHLORINTION, CATALYTIC ADDITION OF CARBON MONOXIDE AND HYDROGEN, SUBSEQUUENT HYDROGENATION AND TREATMENT WITH MOLTEN ALKALI HAVING A MOLECULAR SIZE OF ABOUT C22-C40 AND A PORTION OF ITS ACID CONTENT NEUTRALIZED IN THE FORM OF A METAL SAOP SELECTED FORM THE GROUP CONSISTING OF CALCIUM, SODIUM, POTASSIUM, BARIUM AND STRONTIUM SOAPS, WITH A WAXY MEMBER SELECTED FROM ATHE GROUP CONSISTING OF HARD PARAFFINS MELTING ABOVE ABOUT 70*C., POLYETHYLENES HAVING A MOLECULAR WEIGHT ABOVE 1,000 AND BELOW 10,000, AND MIXTURES THEROF. 